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Glossary

acid a proton (hydrogen ion) donor. atomic orbitals regions of space outside the nucleus
acid–base indicator a substance that changes colour over that can be occupied by one or, at most, two
a narrow range of pH values. electrons. Orbitals are named s, p, d and f. They
acid dissociation constant, Ka the equilibrium constant have different shapes.
for a weak acid: average bond energy a general bond energy value used for
[H+][A–]
Ka = _______ a particular bond, e.g. a C H, when the exact
[HA]
bond energy is not required. Average bond energies
activation energy the minimum energy that colliding
are often used because the strength of a bond between
particles must possess for a successful collision that
two particular types of atom is slightly different in
results in a reaction to take place.
different compounds.
active site (of an enzyme) the ‘pocket’ on an enzyme
Avogadro constant the number of atoms (or ions,
surface where the substrate binds and undergoes
molecules or electrons) in a mole of atoms (or ions,
catalytic reaction.
molecules or electrons): its numerical value
acyl chloride a reactive organic compound related to
is 6.02 × 1023.
a carboxylic acid, with the OH group in the acid
azo dyes coloured compounds formed on the
replaced by a Cl atom, for example ethanoyl chloride,
addition of phenol (or another aryl compound) to
CH3COCl.
a solution containing a diazonium ion. They contain
addition polymerisation the reaction in which monomers
containing carbon-to-carbon double bonds react the N N group.
together to form long-chain molecules called polymers.
addition reaction an organic reaction in which two base a proton (hydrogen ion) acceptor.
477
reactant molecules combine to give a single bidentate ligands that can form two co-ordinate bonds
product molecule. from each ion or molecule to the central transition
adsorption (in catalysis) the first stage in heterogeneous metal ion.
catalysis – molecules of reactants (usually gases) form biofuels renewable fuels, sourced from plant or
bonds with atoms on the surface of the catalyst. animal materials.
alkali a base that is soluble in water. boiling point the temperature at which the vapour
alkaline earth metals the elements in Group 2 of the pressure is equal to the atmospheric pressure.
Periodic Table. Boltzmann distribution a graph showing the
alkanes saturated hydrocarbons with the general formula distribution of energies of the particles in a sample at a
CnH2n+2. given temperature.
alkenes unsaturated hydrocarbons with a carbon–carbon bond energy/bond enthalpy the energy needed to
double bond. Their general formula is CnH2n. break 1 mole of a particular bond in 1 mole of
allotrope different crystalline or molecular forms of the gaseous molecules.
same element. Graphite and diamond are allotropes Born–Haber cycle a type of enthalpy cycle used to
of carbon. calculate lattice energy.
alloy a mixture of two or more metals or a metal with a Brønsted–Lowry theory of acids acids are proton donors
non-metal. and bases are proton acceptors.
amino acid residue an amino acid unit within a buffer solution a solution that minimises changes in
polypeptide chain. pH when moderate amounts of acid or base are
amphoteric able to behave as both an acid and a base. added. Common forms of buffer consist of either a
Aluminium oxide is amphoteric. weak acid and its conjugate base or a weak base and
anion a negatively charged ion. its conjugate acid.
anode the positive electrode.
arenes hydrocarbons containing one or more carbocation an alkyl group carrying a single positive
benzene rings. charge on one of its carbon atoms, e.g. +CH2CH3
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catalyst a substance that increases the rate of a reaction cracking the process in which large, less useful
but remains chemically unchanged itself at the end of hydrocarbon molecules are broken down into smaller,
the reaction. more useful molecules.
cathode the negative electrode.
cation a positively charged ion. dative covalent bond another name for a co-ordinate bond.
chiral centre a carbon atom with four different groups degenerate orbitals atomic orbitals at the same
attached, creating the possibility of optical isomers. energy level.
closed system a system in which matter or energy is not dehydration a reaction in which a water molecule is
lost or gained, e.g. gases in a closed vessel. removed from a molecule, e.g. in the dehydration of an
cofactor a small molecule that is not a substrate but that is
alcohol to give an alkene.
essential for an enzyme-catalysed reaction.
delocalised electrons electrons that are not associated
common ion effect the reduction in the solubility of a
with a particular atom – they can move between three
dissolved salt by adding a compound that has an ion in
or more adjacent atoms.
common with the dissolved salt. This often results in
denaturation the process by which the three-
precipitation of the salt.
dimensional structure of a protein or other biological
competitive inhibition enzyme inhibition by molecules
that bind to the active site, preventing the normal macromolecule is changed, often irreversibly. Relatively
substrate from reacting. They have a structure similar to high temperatures, extremes of pH and organic solvents
the substrate molecule. The inhibition is reversible. often cause denaturation.
complementary base pairing In nucleic acids, bases are desorption the last stage in heterogeneous catalysis.
said to be complementary to each other if they form The bonds holding the molecule(s) of product(s) to
specific hydrogen-bonded pairs. In DNA adenine (A) the surface of the catalyst are broken and the product
always pairs with thymine (T) and cytosine (C) always molecules diffuse away from the surface of the catalyst.
478 pairs with guanine (G). diazotisation the reaction between phenylamine
complex a central transition metal ion surrounded and nitrous acid (nitric(III) acid), HNO2, to give a
by ligands. diazonium salt in the first step in making an azo dye.
compound a substance made up of two or more elements dipeptide the product formed when two amino acids
bonded (chemically joined) together. react together.
condensation the change in state when a vapour changes dipole a separation of charge in a molecule. One end of
to a liquid. the molecule is permanently positively charged and the
condensation reaction a reaction in which two organic other is negatively charged.
molecules join together and in the process eliminate a discharge the conversion of ions to atoms or molecules at
small molecule, such as water or hydrogen chloride. electrodes during electrolysis, for example, during
conjugate pair (acid/base) an acid and base on each side
the electrolysis of concentrated sodium chloride
of an equilibrium equation that are related to each
solution, chlorine is discharged at the anode by the
other by the difference of a proton; e.g. the acid in the
conversion of Cl– ions to Cl atoms, which then combine
forward reaction and the base in the reverse reaction
to form Cl2 molecules.
or the base in the forward reaction and the acid in the
displayed formula a drawing of a molecule that shows all
reverse reaction.
the atoms and bonds within the molecule.
co-ordinate bond a covalent bond in which both electrons
in the bond come from the same atom. disproportionation the simultaneous reduction and
co-ordination number the number of co-ordinate (dative) oxidation of the same species in a chemical reaction.
bonds formed by ligands to the central transition metal dissociation the break-up of a molecule into ions, for
ion in a complex. example, when HCl molecules dissolve in aqueous
coupling reaction when a diazonium ion reacts with an solution, they dissociate completely into H+ and Cl– ions.
alkaline solution of phenol (or similar compound) to disulfide bridge an S S bond formed when the SH
make an azo dye. groups on the side-chain of two cysteine residues in a
covalent bond a bond formed by the sharing of pairs of protein combine. Disulfide bridges help maintain the
electrons between two atoms. tertiary structure of some proteins.
Glossary

DNA (deoxyribonucleic acid) a polymer with a double electrophile a species that can act as an acceptor of a pair
helical structure containing two sugar–phosphate chains of electrons in an organic mechanism.
with nitrogenous bases attached to them. The sequence electrophoresis the separation of charged particles by
of bases forms a code, which is used to form more DNA their different rates of movement in an electric field.
by replication or to encode mRNA (transcription). electrovalent bond another name for an ionic bond.
dot-and-cross diagram a diagram showing the element a substance made of only one type of atom.
arrangement of the outer-shell electrons in an ionic elimination a reaction in which a small molecule, such as
or covalent element or compound. The electrons are H2O or HCl, is removed from an organic molecule.
shown as dots or crosses to show their origin. empirical formula the formula that tells us the simplest
double covalent bond two shared pairs of electrons ratio of the different atoms present in a molecule.
bonding two atoms together. endothermic term used to describe a reaction in which
dynamic (equilibrium) in an equilibrium mixture, energy is absorbed from the surroundings: the enthalpy
molecules of reactants are being converted to change is positive.
products at the same rate as products are being energy levels (of electrons) the regions at various
converted to reactants. distances from the nucleus in which electrons have a
particular amount of energy. Electrons further from the
electrochemical cell two half-cells in separate nucleus have more energy. See principal quantum shells.
compartments joined by a salt bridge. When the poles enhanced global warming the increase in average
of the half-cells are joined by a wire, electrons travel temperatures around the world as a consequence of
in the external circuit from the half-cell with the more the huge increase in the amounts of CO2 and other

O
negative E value to the half-cell with the more greenhouse gases produced by human activity.

enthalpy change of atomisation ΔH at ; the enthalpy
O
positive E —O value.
electrode a rod of metal or carbon (graphite) which change when 1 mole of gaseous atoms is formed from
conducts electricity to or from an electrolyte. its element under standard conditions.

O 479
electrode potential the voltage measured for a half-cell enthalpy change of hydration ΔHhyd; the enthalpy change
compared with another half-cell. when 1 mole of a specified gaseous ion dissolves in
electrolysis the decomposition of a compound into its sufficient water to form a very dilute solution.

O
elements by an electric current. enthalpy change of solution ΔH sol ; the energy absorbed
electrolyte a molten ionic compound or an aqueous or released when 1 mole of an ionic solid dissolves in
solution of ions that is decomposed during sufficient water to form a very dilute solution.
electrolysis. enthalpy change the energy transferred in a chemical
reaction (symbol ΔH).
electron tiny subatomic particles found in orbitals around
enthalpy cycle a diagram showing alternative routes
the nucleus. They have a negative charge but have
between reactants and products that allows the
negligible mass.
— determination of one enthalpy change from other
electron affinity (first electron affinity) ΔH ea1 ; the
O

known enthalpy changes by using Hess’s law.


enthalpy change when 1 mole of electrons is added to
enthalpy profile diagram a diagram showing the
1 mole of gaseous atoms to form 1 mole of gaseous
enthalpy change from reactants to products along the
1– ions under standard conditions. reaction pathway.

O
electron affinity (second electron affinity) ΔH ea2 ; the entropy a measure of the dispersal of energy or disorder of
enthalpy change when 1 mole of electrons is added to a system. The system becomes energetically more stable
1 mole of gaseous 1– ions to form 1 mole of gaseous when disordered.
2– ions under standard conditions. enzyme a protein molecule that is a biological catalyst.
electronegativity the ability of an atom to attract the Most act on a specific substrate.
bonding electrons in a covalent bond. enzyme activity a measure of the rate at which substrate is
electronic configuration a way of representing the converted to product in an enzyme-catalysed reaction.
arrangement of the electrons in atoms showing the equilibrium constant a constant calculated from the
principal quantum shells, the subshells and the number equilibrium expression for a reaction.
of electrons present, e.g. 1s2 2s2 2p3. The electrons may equilibrium expression a simple relationship that links
also be shown in boxes. Kc to the equilibrium concentrations of reactants and
electropherogram the physical results of electrophoresis. products and the stoichiometric equation.
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equilibrium reaction a reaction that does not go to functional group an atom or group of atoms in an organic
completion and in which reactants and products are molecule that determine the characteristic reactions of a
present in fixed concentration ratios. homologous series.
esterification the reaction between an alcohol and a
carboxylic acid (or acyl chloride) to produce an ester gene a length of DNA that carries a code for making a
and water. particular protein.
eutrophication an environmental problem caused by general formula a formula that represents a homologous
fertilisers leached from fields into rivers and lakes. The series of compounds using letters and numbers; e.g.
fertiliser then promotes the growth of algae on the the general formula for the alkanes is CnH2n+2. By
surface of water. When the algae die, bacteria thrive substituting a number for n in the general formula you
and use up the dissolved oxygen in the water, killing get the molecular formula of a particular compound in
aquatic life. that homologous series.
exothermic the term used to describe a reaction in which general gas equation an equation relating the volume of a
energy is released to the surroundings: the enthalpy gas to the temperature, pressure and number of moles
change is negative. of gas. Also called the ideal gas equation.
pV = nRT
Faraday constant the charge carried by 1 mole of electrons genetic code a code made up of sets of three consecutive
(or 1 mole of singly charged ions). It has a value of nitrogenous bases that provides the information to
96 500 coulombs per mol (C mol–1). make specific proteins.
Faraday’s laws first law: the mass of a substance produced genetic engineering the deliberate alteration of one or
at an electrode during electrolysis is proportional to the more bases in the DNA of an organism, leading to an
quantity of electricity passed in coulombs. Second law: altered protein with improved properties. Scientists
the number of Faradays needed to discharge 1 mole of hope to be able to use genetic engineering to eliminate
480 an ion at an electrode equals the number of charges on genetic diseases which are caused by mutations in DNA.
the ion. genetic fingerprinting a technique based on matching the
feasibility (of reaction) the likelihood or not of a reaction minisatellite regions of a person’s DNA to a database of
occurring when reactants are mixed. We can use E

O reference samples.
values to assess the feasibility of a reaction. giant molecular structure/giant covalent
Fehling’s solution an alkaline solution containing structure structures having a three-dimensional
copper(II) ions used to distinguish between aldehydes network of covalent bonds throughout the
and ketones. A positive test is one in which the clear whole structure.
blue solution gives a red/orange precipitate when Gibbs free energy the energy change that takes into
warmed with aldehydes, but no change is observed account both the entropy change of a reaction and
with ketones. enthalpy change. Reactions are likely to be feasible if
fragmentation the breaking up of a molecule into smaller the value of the Gibbs free energy change of reaction
is negative. The Gibbs free energy change of reaction is
parts by the breaking of covalent bonds in a mass
given by the relationship
spectrometer.

O —
O —
O
free energy see Gibbs free energy. ΔG = ΔH – TΔS
free radical very reactive atom or molecule that has a GLC gas–liquid chromatography.
single unpaired electron. GLC/MS a technique in which a mass spectrometer is
free-radical substitution the reaction in which halogen connected directly to a gas–liquid chromatograph to
atoms substitute for hydrogen atoms in alkanes. The identify the components in a mixture.
mechanism involves steps in which reactive free radicals
are produced (initiation), regenerated (propagation) haemoglobin the iron-containing protein found in red
and consumed (termination). blood cells that transports oxygen around the body.
Friedel–Crafts reaction the electrophilic substitution of half-cell half of an electrochemical cell. The half-cell with

an alkyl or acyl group into a benzene ring. O
the more negative E value supplies electrons. The half-

fuel cell a source of electrical energy that comes directly O
cell with the more positive E value receives electrons.
from the energy stored in the chemicals in the cell, one half-equation in a redox reaction, an equation showing
of which is oxygen (which may come from the air). either an oxidation or a reduction.
Glossary

half-life the time taken for the amount (or concentration) ionic product of water, Kw the equilibrium constant for
of the limiting reactant in a reaction to decrease to half the ionisation of water.
its value.
Kw = [H+][OH–]
halogens Group 17 elements.
Hess’s law the total enthalpy change for a chemical ionisation energy, ΔHi the energy needed to remove
reaction is independent of the route by which the 1 mole of electrons from 1 mole of atoms of an element
reaction takes place. in the gaseous state to form 1 mole of gaseous ions.
heterogeneous catalysis the type of catalysis in which the isotopes atoms of an element with the same number of
catalyst is in a different phase from the reactants. For protons but different numbers of neutrons.
example, iron in the Haber process.
homogeneous catalysis the type of catalysis in which kinetic theory the theory that particles in gases and
the catalyst and reactants are in the same phase. For liquids are in constant movement. The kinetic theory
example, sulfuric acid catalysing the formation of an can be used to explain the effect of temperature and
ester from an alcohol and carboxylic acid. pressure on the volume of a gas as well as rates of
HPLC high-performance liquid chromatography. chemical reactions.
hybridisation of atomic orbitals the process of mixing
atomic orbitals so that each has some character of each lattice a regularly repeating arrangement of ions, atoms or
of the orbitals mixed. molecules in three dimensions.
hydrocarbon a compound made up of carbon and lattice energy the enthalpy change when 1 mole of an
hydrogen only. ionic compound is formed from its gaseous ions under
hydrogen bond the strongest type of intermolecular force standard conditions.
– it is formed between molecules having a hydrogen le Chatelier’s principle when any of the conditions
atom bonded to one of the most electronegative affecting the position of equilibrium are changed,
elements (F, O or N). the position of that equilibrium shifts to minimise 481
hydrolysis the breakdown of a compound by water, which the change.
is often speeded up by reacting with acid or alkali. ligand a molecule or ion with one or more lone pairs of
hydrophobic the non-polar part of a molecule that has no electrons available to donate to a transition metal ion.
attraction for water molecules (‘water hating’). lock-and-key mechanism a model used to explain why
hydroxynitrile an organic compound containing both an enzymes are so specific in their activity. It is suggested
OH and a CN group, e.g. 2-hydroxypropanenitrile, that the active site of the enzyme has a shape into which
CH3CH(OH)CN. the substrate fits exactly – rather like a particular key
fits a particular lock.
ideal gas a gas whose volume varies in proportion to the lone pairs (of electrons) pairs of electrons in the outer
temperature and in inverse proportion to the pressure. shell of an atom that are not bonded.
Noble gases such as helium and neon approach ideal
behaviour because of their low intermolecular forces. mass number see nucleon number.
infra-red spectroscopy a technique for identifying mass spectrometer an instrument for finding the relevant
compounds based on the change in vibrations of isotopic abundance of elements and to help identify
particular atoms when infra-red radiation of specific unknown organic compounds.
frequencies is absorbed metabolism the series of linked chemical reactions taking
initiation step the first step in the mechanism of free- place in living organisms.
radical substitution of alkanes by halogens. It involves metalloid elements that have a low electrical conductivity
the breaking of the halogen–halogen bond by UV light at room temperature but whose conductivity increases
from the Sun. with increasing temperature. Metalloids are found in a
intermolecular forces the weak forces between molecules. diagonal band running from the top left to nearly the
ion polarisation the distortion of the electron cloud on bottom right of the p-block in the Periodic Table.
an anion by a neighbouring cation. The distortion is mobile phase the solvent in the chromatography process,
greatest when the cation is small and highly charged. which moves through the column or over the paper or
ionic bond the electrostatic attraction between oppositely thin layer.
charged ions. molar mass the mass of a mole of substance in grams.
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mole the unit of amount of substance. It is the amount of open system a system in which matter is lost or gained,
substance that has the same number of particles (atoms, e.g. a mixture of solids and gases in an open beaker.
ions, molecules or electrons) as there are atoms in optical isomers stereoisomers that exist as two non-
exactly 12 g of the carbon-12 isotope. superimposable mirror images.
molecular formula the formula that tells us the actual optical resolution the separation of optically active
numbers of each type of atom in a molecule. isomers (enantiomers) from a mixture.
molecular ion the ion that is formed by the loss of an order of reaction the power to which the concentration
electron from the original complete molecule during of a reactant is raised in the rate equation. If the
mass spectrometry and that gives us the relative concentration does not affect the rate, the reaction is
molecular mass of an unknown compound.
zero order. If the rate is directly proportional to the
monodendate ligands, such as water and ammonia, that
reactant concentration, the reaction is first order. If the
can form only one co-ordinate bond from each ion or
rate is directly proportional to the square of the reactant
molecule to the central transition metal ion.
monomer a small, reactive molecule that reacts to make concentration, the reaction is second order.
long-chain molecules called polymers. oxidation the addition of oxygen, removal of electrons or
increase in oxidation number of a substance; in organic
nanotechnology the design and production of machines chemistry refers to a reaction in which oxygen atoms
that are so small we measure them in nanometres (nm), are added to a molecule and/or hydrogen atoms are
where 1 nm = 1 × 10–9 m. removed from a molecule.
Nernst equation an equation used to predict oxidation number (oxidation state) a number given to
quantitatively how the value of an electrode potential an atom in a compound that describes how oxidised or
varies with the concentration of the aqueous ion. reduced it is.
neutron a subatomic particle found in the nucleus of an oxidising agent a reactant that increases the
atom. It has no charge and has the same mass as oxidation number of (or removes electrons from)
482 a proton. another reactant.
nitrogenous bases nitrogen-containing bases found in
DNA and RNA. In DNA they are adenine (A), guanine
partial pressure the pressure that an individual gas
(G), thymine (T) and cytosine (C). In RNA uracil (U)
contributes to the overall pressure in a mixture of gases.
replaces thymine.
partition coefficient the ratio of the concentrations of
NMR nuclear magnetic resonance spectroscopy.
non-degenerate orbitals atomic orbitals that have been a solute in two different immiscible solvents when an
split to occupy slightly different energy levels. equilibrium has been established.
non-polar (molecule) a molecule with no separation peptide bond the link between the amino acid residues
of charge; it will not be attracted to a positive or in a polypeptide or protein chain. The link is formed
negative charge. by a condensation reaction between the NH2 group
nucleon number the total number of protons and of one amino acid and the COOH group of another
neutrons in the nucleus of an atom. amino acid.
nucleophile species that can act as a donor of a pair periodicity the repeating patterns in the physical and
of electrons. chemical properties of the elements across the periods
nucleophilic addition the mechanism of the reaction of the Periodic Table.
in which a nucleophile attacks the carbon atom in a permanent dipole–dipole forces a type of intermolecular
carbonyl group and adds across the C O bond, e.g. force between molecules that have permanent dipoles.
aldehydes or ketones reacting with hydrogen cyanide.
pH the hydrogen ion concentration expressed as a
nucleotide a compound consisting of a nitrogenous base,
logarithm to base 10.
a sugar (ribose or deoxyribose) and a phosphate group.
Nucleotides form the basic structural units of DNA pH = –log10[H+]
and RNA.
pi (π) bonds multiple covalent bonds involving the
nucleus the small dense core at the centre of every
sideways overlap of p atomic orbitals.
atom, containing protons (positively charged) and
pKa values of Ka expressed as a logarithm to base 10.
neutrons (no charge). Nuclei are therefore always
positively charged. pKa = –log10Ka
Glossary

polar (covalent bond) a covalent bond in which the two rate-determining step the slowest step in a
bonding electrons are not shared equally by the atoms reaction mechanism.
in the bond. The atom with the greater share of the real gases gases that do not obey the ideal gas law,
electrons has a partial negative charge, δ–, and the other especially at low temperatures and high pressures.
has a partial positive charge, δ+. redox reaction a reaction in which oxidation and
polarising power (of a cation) the ability of a cation to reduction take place at the same time.
attract electrons and distort an anion. reducing agent a reactant that decreases the oxidation
polyamides polymers whose monomers are bonded to number of (or adds electrons to) another reactant.
each other via the amide link, CONH . reduction the removal of oxygen, addition of electrons
polyesters polymers whose monomers are bonded to each or decrease in oxidation number of a substance; in
other via the ester link, COO . organic chemistry it is the removal of oxygen atoms
polymer a long-chain molecule made up of many from a molecule and/or the addition of hydrogen atoms
repeating units. to a molecule.
polypeptides natural polymers whose monomers are relative atomic mass the weighted average mass of
bonded to each other via the amide link, CONH , the atoms of an element, taking into account the
and whose monomers are amino acids. proportions of naturally occurring isotopes, measured
on a scale on which an atom of the carbon-12 isotope
primary alcohol an alcohol in which the carbon atom
has a mass of exactly 12 units.
bonded to the OH group is attached to one other
relative formula mass the mass of one formula unit of a
carbon atom (or alkyl group).
compound measured on a scale on which an atom of
primary structure (of proteins) the sequence of amino
the carbon-12 isotope has a mass of exactly 12 units.
acids in a polypeptide chain.
relative isotopic mass the mass of a particular isotope
principal quantum shells, n regions at various distances
of an element on a scale in which an atom of the
from the nucleus that may contain up to a certain
carbon-12 isotope has a mass of exactly 12 units.
number of electrons. The first quantum shell contains
relative molecular mass the mass of a molecule measured 483
up to 2 electrons, the second up to 8 and the third up on a scale in which an atom of the carbon-12 isotope
to 18. has a mass of exactly 12 units.
propagation step a step in a free-radical mechanism in residue see amino acid residue.
which the radicals formed can then attack reactant retention time the time taken for a component in a
molecules generating more free-radicals, and so on. mixture to travel through the column in GLC or HPLC.
protein condensation polymer formed from amino reversible reaction a reaction in which products can be
acids and joined together by peptide bonds. Proteins changed back to reactants by reversing the conditions.
can be structural (e.g. cartilage), catalysts (enzymes), Rf value the ratio of the distance a component has
hormones (e.g. insulin) or antibodies. travelled compared with the distance travelled by the
proton a positively charged subatomic particle in solvent front during paper chromatography or TLC.
the nucleus.
salt bridge a piece of filter paper soaked in potassium
rate constant the proportionality constant in the rate nitrate solution used to make electrical contact between
equation (see rate equation). the half-cells in an electrochemical cell.
rate equation an equation showing the relationship saturated hydrocarbons compounds of hydrogen and
between the rate constant and the concentrations of carbon only in which the carbon–carbon bonds are
those reactants that affect the rate of reaction. The all single covalent bonds, resulting in the maximum
general form of the rate equation is: number of hydrogen atoms in their molecules.
rate = k[A]m[B]n secondary alcohol an alcohol in which the carbon atom
where k is the rate constant, [A] and [B] are the bonded to the OH group is attached to two other
concentrations of those reactants that affect the rate of carbon atoms (or alkyl groups).
reaction, m is the order of the reaction with respect to A secondary structure (of proteins) the second level of
and n is the order of reaction with respect to B. protein structure. The folding of a polypeptide chain
rate of reaction a measure of the rate at which reactants into specific structures (e.g. α-helix and β-pleated
are used up or the rate at which products are formed. sheet), which are stabilised by hydrogen bonds formed
The units of rate are mol dm–3 s–1. between CO and NH groups in peptide bonds.
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shielding the ability of inner shells of electrons to standard conditions conditions of temperature and
reduce the effective nuclear charge on electrons in the pressure that must be the same in order to compare
outer shell. moles of gases or enthalpy changes accurately. Standard
sigma (σ) bonds single covalent bonds, formed by the conditions are a pressure of 105 pascals (100 kPa) and a
‘end-on’ overlap of atomic orbitals. temperature of 298 K (25 °C).
single covalent bond a shared pair of electrons bonding standard electrode potential the electrode potential of
two atoms together. a half-cell when measured with a standard hydrogen
skeletal formula a simplified version of the displayed electrode as the other half-cell.
formula that has all the symbols for carbon and standard enthalpy change an enthalpy change that takes
5
hydrogen atoms removed, as well as the carbon to place under the standard conditions of pressure (10 Pa)
and temperature (298 K).
hydrogen bonds. The carbon to carbon bonds are left in
standard hydrogen electrode a half-cell in which
place as are the bonds to other atoms.
hydrogen gas at a pressure of 1 atmosphere (101 kPa)
SN1 mechanism the steps in a nucleophilic substitution
bubbles into a solution of 1.00 mol dm–3 H+ ions.
reaction in which the rate of the reaction (which is This electrode is given a standard electrode potential
determined by the slow step in the mechanism) involves of 0.00 V. All other standard electrode potentials are
only the organic reactant, e.g. in the hydrolysis of a measured relative to this value.
tertiary halogenoalkane. state symbol a symbol used in a chemical equation that
SN2 mechanism the steps in a nucleophilic substitution describes the state of each reactant and product: (s) for
reaction in which the rate of the reaction (which is solid, (l) for liquid, (g) for gas and (aq) for substances in
determined by the slow step in the mechanism) involves aqueous solution.
two reacting species, e.g. in the hydrolysis of a primary stationary phase the immobile phase in chromatography
halogenoalkane. that the mobile phase passes over or through.
solubility product, Ksp the equilibrium expression Examples are the surface of the thin-layer particles in
484
showing the product of the concentrations of each ion TLC or the involatile liquid adsorbed onto the column
in a saturated solution of a sparingly soluble salt at in GLC or HPLC.
298 K, raised to the power of the relative concentrations: stereoisomers compounds whose molecules have the
same atoms bonded to each other but with different
Ksp = [C y+(aq)]a[A x–(aq)]b arrangements of the atoms in space.
where a is the number of C y+ ions in one formula unit stoichiometry the mole ratio of the reactants and products
of the compound and b is the number of Ax– ions in one in the balanced equation for a reaction.
strong acid/base an acid or base that is (almost)
formula unit of the compound.
completely ionised in water.
solute a substance that is dissolved in a solution.
structural formula the formula that tells us about the
specific most enzymes are described as specific because
atoms bonded to each carbon atom in an organic
they will only catalyse one reaction involving one
molecule, e.g. CH3CH CH2.
particular molecule or pair of molecules.
structural isomers compounds with the same molecular
spectator ions ions present in a reaction mixture that do formula but different structural formulae.
not take part in the reaction. subshells regions within the principal quantum shells
spin-pair repulsion electrons repel each other as they where electrons have more or less energy depending on
have the same charge. Electrons arrange themselves their distance from the nucleus. Subshells are given the
so that they first singly occupy different orbitals in the letters s, p, d and f.
same sublevel. After that they pair up with their spins substitution a reaction that involves the replacement of
opposed to each other. one atom, or group of atoms, by another.
splitting pattern the pattern of peaks that main signals are substrate a molecule that fits into the active site of an
divided into in high-resolution NMR. enzyme and reacts.
stability constant, Kstab the equilibrium constant for the successive ionisation energy ΔHi1, ΔHi2, etc.: the energy
formation of the complex ion in a solvent from its required to remove the first, then the second, then the
constituent ions or molecules. third electrons and so on from a gaseous atom or ion,
standard cell potential the difference in standard producing an ion with one more positive charge each
electrode potential between two half-cells. time. Measured in kJ per mole of ions produced.
Glossary

surroundings in enthalpy changes, anything other than two-way chromatography a technique used in paper
the chemical reactants and products, for example the or thin-layer chromatography in which one spot of a
solvent, the test tube in which the reaction takes place, mixture is placed at the corner of a square sheet and
the air around the test tube. is developed in the first solvent as usual. The sheet is
then turned through 90° and developed in the second
termination step the final step in a free-radical solvent, giving a better separation of components
mechanism in which two free radicals react together to having similar Rf values.
form a molecule.
tertiary alcohol an alcohol in which the carbon atom unsaturated hydrocarbons compounds of hydrogen and
bonded to the OH group is attached to three other carbon only whose molecules contain carbon-to-carbon
carbon atoms (or alkyl groups). double bonds (or triple bonds).
tertiary structure (of proteins) the third level of protein
structure. It involves further folding of the polypeptide van der Waals’ forces the weak forces of attraction
chain, which is stabilised by interactions between the between molecules caused by the formation of
amino acid side-chains (ionic interactions, hydrogen temporary dipoles.
bonding, van der Waals’ forces and disulfide bonds). vaporisation the change in state when a liquid changes
titre in a titration, the final burette reading minus the to vapour.
initial burette reading. vapour pressure the pressure exerted by a vapour in
TLC thin-layer chromatography. equilibrium with a liquid.
TMS tetramethylsilane. An inert, volatile liquid used as a
reference in NMR, given a chemical shift of zero. weak acid/base an acid or base that is only slightly ionised
Tollens’ reagent an aqueous solution of silver nitrate in water.
in excess ammonia solution, sometimes called
ammoniacal silver nitrate solution. It is used to X-ray crystallography an analytical technique that uses
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distinguish between aldehydes and ketones. It gives the diffraction pattern of X-rays passed through a solid
a positive ‘silver mirror’ test when warmed with sample to elucidate its structure.
aldehydes, but no change is observed with ketones.
triple covalent bond three shared pairs of electrons
bonding two atoms together.